EP0051328B1 - Process for the preparation of alcohols - Google Patents

Process for the preparation of alcohols Download PDF

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Publication number
EP0051328B1
EP0051328B1 EP81201148A EP81201148A EP0051328B1 EP 0051328 B1 EP0051328 B1 EP 0051328B1 EP 81201148 A EP81201148 A EP 81201148A EP 81201148 A EP81201148 A EP 81201148A EP 0051328 B1 EP0051328 B1 EP 0051328B1
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EP
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Prior art keywords
acid
alpha
olefinically unsaturated
unsaturated hydrocarbon
water
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Expired
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EP81201148A
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German (de)
French (fr)
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EP0051328A1 (en
Inventor
Lynn Henry Slaugh
Carl Lesley Willis
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C07C29/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis

Definitions

  • the invention relates to a process for the preparation of alcohols by reacting an olefinically unsaturated hydrocarbon with water in the presence of a catalyst.
  • the present invention provides a process for the preparation of alcohols, which comprises reacting an olefinically unsaturated hydrocarbon with water in the presence of an alpha-hydroxysulphonic acid prepared by reacting a carbonyl compound of the general formula R 1 R 2 CO, wherein R 1 and R 2 are individually hydrogen or a substituted or unsubstituted hydrocarbyl group containing up to 7 carbon atoms, with sulphur dioxide and water.
  • a unique feature of these alpha-hydroxysulphonic acids is the easy reversibility of the acid formation according to equation (1), i.e. when heated sulphur dioxide is liberated and the solution becomes neutral. Decreasing the sulphur dioxide pressure for this system induces the same effect. This reversibility provides for the method utilized to remove unutilized acid from the reaction streams. By increasing the temperature or lowering the pressure, the sulphur dioxide can be driven off leaving the carbonyl compound and water. These latter materials can then be removed by conventional means, such as distillation.
  • olefinically unsaturated hydrocarbons are hydrated by the present invention, including linear, branched or cyclic hydrocarbons and including alpha or internal olefins.
  • Suitable compounds are C 2 to C 22 mono-olefinically unsaturated hydrocarbons.
  • the present process is as applicable to the detergent range olefins, i.e. C s through C 22 , as it is for the lower ranged olefins, C 2 through C 7 .
  • the invention is particularly suited for the lower range C 2 through C 5 olefins. Mixtures of olefins may be used.
  • the present invention is particularly advantageous for hydrating propylene to isopropanol.
  • Olefinically unsaturated compounds in admixture with non-olefinic material, e.g. alkanes are also suitably used, and a particularly useful feedstock for the present invention is a so-called BB or butane/butene stream which is mainly a mixture of isobutane with isomeric butenes.
  • the products of the present invention are the alcohols corresponding to the hydration products of the olefinically unsaturated materials used.
  • the amounts of initial reactants used in the present invention may vary between wide limits.
  • the moles of water initially present should be equal at least to the moles of unsaturated bonds in the olefin to be hydrated.
  • the molar ratio of olefin to water will range from 1:1 to 1:50, preferably from 1:1 to 1:20, and most preferably from 1:1 to 1:10.
  • the molar ratio of alpha-hydroxysulphonic acid to olefin will range from 1:100 to 5:1, preferably from 1:10 to 2:1.
  • the temperature at which the reaction is carried out will depend on several variables. One significant variable would be the specific reactant alcohol combination utilized. The higher molecular olefin and alcohols would require higher temperatures in order to maintain reasonable viscosities of the reacting and reactant materials.
  • the particular alpha-hydroxysulphonic acid ultilized will also determine reaction temperatures and pressures. The reaction temperatures and pressures chosen should be such as to maintain a high proportion of alpha-hydroxysulphonic acid in the reaction mixture. Temperatures may range from -20°C to 200°C, preferably from 0°C to 100°C. Preferred pressures range from 0.5 to 5 kPa.
  • alpha-hydroxymethanesulphonic acid begins to lose some of its efficiency above about 100°C (at one kPa) because of the equilibrium shift above this temperature to the component parts, whereas alpha-hydroxyethanesulphonic acid begins to lose some of its efficiency above about 40°C (at one kPa).
  • Contact times may range from 0.01 to 100 h, preferably from 0.1 to 50 h.
  • the contact of the olefin- containing hydrocarbon phase with the aqueous acid-containing phase involves intimate mixing of two immiscible phases by techniques that are well-known in the art.
  • Inert solvents may also be used in the process of the present invention.
  • non-polar organic solvents such as alkanes can be utilized to lower the viscosity of the reactant olefin component.
  • Organic solvents which possess both hydrocarbon and water solubility may also be used. These latter materials comprise, for example, alcohols, ethers, ketones, acids and sulphones.
  • the reaction product is worked up by any convenient technique.
  • the hydration reaction product mixture can be subjected to vacuum to strip off the sulphur dioxide from the alpha-hydroxysulphonic acid, and then subsequently stripped by conventional techniques to remove unreacted olefinically unsaturated compounds, carbonyl compounds, and any other non-olefinic material present.
  • the removed material may be recycled directly to the hydration reactor or the carbonyl compounds can be extracted and later combined with S0 2 and water to form the alpha-hydroxysulphonic acid which is then recycled to the hydration reactor.
  • the stripped reaction product may then be distilled to produce the alcohol product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  • The invention relates to a process for the preparation of alcohols by reacting an olefinically unsaturated hydrocarbon with water in the presence of a catalyst.
  • The hydration of olefins using as catalysts sulphuric and sulphonic acids is known (see, for example, British patent specification 1,518,461). These conventional catalysts have the disadvantage that considerable amounts of by-products such as ketones are produced.
  • It has now been found that the formation of such by-products is minimized by the use, as catalyst, of an alpha-hydroxysulphonic acid, prepared by reacting a carbonyl compound with sulphur dioxide and water.
  • Accordingly, the present invention provides a process for the preparation of alcohols, which comprises reacting an olefinically unsaturated hydrocarbon with water in the presence of an alpha-hydroxysulphonic acid prepared by reacting a carbonyl compound of the general formula R1R2CO, wherein R1 and R2 are individually hydrogen or a substituted or unsubstituted hydrocarbyl group containing up to 7 carbon atoms, with sulphur dioxide and water.
  • The reaction by which the alpha-hydroxysulphonic acids used as catalysts in the present process are prepared may be represented by the following general equation:
    Figure imgb0001
  • Illustrative examples of carbonyl compounds useful to prepare the alpha-hydroxysulphonic acids used in this invention are found, where:
    • R1 = R2 = H (formaldehyde)
    • R1 = H, R2 = CH3 (acetaldehyde)
    • R1 = H, R2 = CH(CH3)2 (i-butyraldehyde)
    • R1 = H, R2 = CCHCHCHO (furfural)
    • R1 = H, R2 = C(CH)4C(OH) (salicylaldehyde)
    • R1 = H, R2 = C(CH)4CH (benzaldehyde)
    • R1 = R2 = CH3 (acetone)
    • R1 = CH3, R2 = CHZCH3 (methyl ethyl ketone)
    • R1 = CH3, R2 = CHC(CH3)2 (mesityl oxide)
    • R1 = CH3, R2 = CH2CH(CH3)2 (methyl i-butyl ketone)
    • R1, R2 = (CH2)5 (cyclohexanone)
    • or R1 = CH3, R2 = CH2CI (chloroacetone)
  • A unique feature of these alpha-hydroxysulphonic acids is the easy reversibility of the acid formation according to equation (1), i.e. when heated sulphur dioxide is liberated and the solution becomes neutral. Decreasing the sulphur dioxide pressure for this system induces the same effect. This reversibility provides for the method utilized to remove unutilized acid from the reaction streams. By increasing the temperature or lowering the pressure, the sulphur dioxide can be driven off leaving the carbonyl compound and water. These latter materials can then be removed by conventional means, such as distillation.
  • Various olefinically unsaturated hydrocarbons are hydrated by the present invention, including linear, branched or cyclic hydrocarbons and including alpha or internal olefins. Suitable compounds are C2 to C22 mono-olefinically unsaturated hydrocarbons. The present process is as applicable to the detergent range olefins, i.e. Cs through C22, as it is for the lower ranged olefins, C2 through C7. The invention is particularly suited for the lower range C2 through C5 olefins. Mixtures of olefins may be used. Specific examples include ethylene, propylene, butenes, pentenes, hexenes, cyclohexenes, heptenes, octenes, nonenes, dodecenes, pentadecenes and octadecenes. The present invention is particularly advantageous for hydrating propylene to isopropanol. Olefinically unsaturated compounds in admixture with non-olefinic material, e.g. alkanes are also suitably used, and a particularly useful feedstock for the present invention is a so-called BB or butane/butene stream which is mainly a mixture of isobutane with isomeric butenes. The products of the present invention are the alcohols corresponding to the hydration products of the olefinically unsaturated materials used.
  • The amounts of initial reactants used in the present invention may vary between wide limits. The moles of water initially present should be equal at least to the moles of unsaturated bonds in the olefin to be hydrated. The molar ratio of olefin to water will range from 1:1 to 1:50, preferably from 1:1 to 1:20, and most preferably from 1:1 to 1:10. The molar ratio of alpha-hydroxysulphonic acid to olefin will range from 1:100 to 5:1, preferably from 1:10 to 2:1.
  • The temperature at which the reaction is carried out will depend on several variables. One significant variable would be the specific reactant alcohol combination utilized. The higher molecular olefin and alcohols would require higher temperatures in order to maintain reasonable viscosities of the reacting and reactant materials. The particular alpha-hydroxysulphonic acid ultilized will also determine reaction temperatures and pressures. The reaction temperatures and pressures chosen should be such as to maintain a high proportion of alpha-hydroxysulphonic acid in the reaction mixture. Temperatures may range from -20°C to 200°C, preferably from 0°C to 100°C. Preferred pressures range from 0.5 to 5 kPa. The use of the lower molecular weight alpha-hydroxysulphonic acids will result in more optimal utilization of higher temperatures than would the use of the higher molecular weight acids. For example, alpha-hydroxymethanesulphonic acid begins to lose some of its efficiency above about 100°C (at one kPa) because of the equilibrium shift above this temperature to the component parts, whereas alpha-hydroxyethanesulphonic acid begins to lose some of its efficiency above about 40°C (at one kPa). Contact times may range from 0.01 to 100 h, preferably from 0.1 to 50 h. The contact of the olefin- containing hydrocarbon phase with the aqueous acid-containing phase involves intimate mixing of two immiscible phases by techniques that are well-known in the art.
  • Inert solvents may also be used in the process of the present invention. For example, non-polar organic solvents such as alkanes can be utilized to lower the viscosity of the reactant olefin component. Organic solvents which possess both hydrocarbon and water solubility may also be used. These latter materials comprise, for example, alcohols, ethers, ketones, acids and sulphones.
  • The reaction product is worked up by any convenient technique. For example, the hydration reaction product mixture can be subjected to vacuum to strip off the sulphur dioxide from the alpha-hydroxysulphonic acid, and then subsequently stripped by conventional techniques to remove unreacted olefinically unsaturated compounds, carbonyl compounds, and any other non-olefinic material present. The removed material may be recycled directly to the hydration reactor or the carbonyl compounds can be extracted and later combined with S02 and water to form the alpha-hydroxysulphonic acid which is then recycled to the hydration reactor. The stripped reaction product may then be distilled to produce the alcohol product.
  • The invention will be illustrated by reference to the following Example, which should not be construed as limiting the invention.
    • Example
  • In a typical preparatio'n of alpha-hydroxymethanesulphonic acid, 30 g of sulphur dioxide were condensed (dry ice/acetone bath) into a 200 ml Fisher-Porter pressure bottle. The reaction vessel was opened and slightly less than one equivalent of aqueous formaldehyde solution (37%w H2CO) was added. The pressure bottle was sealed and the mixture warmed to room temperature. The mixture was stirred vigorously overnight and then vented (S02) to the atmosphere. Analysis of the resulting aqueous phase (potentiometric titration with NaOH/H20) found 5M alpha-hydroxymethanesulphonic acid and a trace of sulphur dioxide. The solution could be stored for up to about four weeks in the pressure bottle without loss in activity.
  • In a typical reaction 11 g (260 mmol) of propylene, 66 g (3600 mmol) of water and 270 mmol of acid catalyst were added to a 300 ml stainless steel autoclave. The reactor was heated to 85°C for the indicated time and initial pressure. The results determined by gaschromatography analysis are shown in Table I below. The sulphuric acid catalyst was noted to form sulphates and the p-toluenesulphonic acid catalyst was noted to have oxidized isopropyl alcohol to acetone. Neither of these by-products was noted with the alpha-hydroxysulphonic acid catalyst.
    Figure imgb0002
  • Comparative experiments were carried out without the use of an alpha-hydroxysulphonic acid. The results are given in Table II below.
  • Figure imgb0003
  • Repeating the above experiment with propylene on 1-pentene and 1-dodecene utilizirig alpha-hydroxymethanesulphonic acid as the catalyst gave similarly satisfactory yields of the corresponding alcohols, which were considerably higher than those obtained with the catalysts mentioned in Table II.

Claims (8)

1. A process for the preparation of alcohols, which comprises reacting an olefinically unsaturated hydrocarbon with water in the presence of a sulphonic group(s) - containing characterised in that the reaction is carried out in the presence of an alpha-hydroxysulphonic acid prepared by reacting a carbonyl compound of the general formula R1R2CO, wherein R1 and R2 are individually hydrogen or a substituted or unsubstituted hydrocarbyl group containing up to 7 carbon atoms, with sulphur dioxide and water.
2. A process as claimed in claim 1, wherein the initial molar ratio of olefinically unsaturated hydrocarbon to water ranges from 1:1 to 1:10.
3. A process as claimed in claim 1 or 2, wherein the.initial molar ratio of acid to hydrocarbon ranges from 1:10 to 2:1.
4. A process as claimed in any one of claims 1-3, wherein the olefinically unsaturated hydrocarbon contains 2-22 carbon atoms.
5. A process as claimed in claim 4, wherein the olefinically unsaturated hydrocarbon contains 2-7 carbon atoms.
6. A process as claimed in claims 4 and 5, wherein the olefinically unsaturated hydrocarbon is propylene.
7. A process as claimed in any one of claims 1-6, wherein the acid is alpha-hydroxymethanesulphonic acid.
8. A process as claimed in any one of claims 1-7, wherein the process is carried out at a temperature ranging from 0 to 100°C.
EP81201148A 1980-11-05 1981-10-15 Process for the preparation of alcohols Expired EP0051328B1 (en)

Applications Claiming Priority (2)

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US06/204,677 US4306101A (en) 1980-11-05 1980-11-05 Olefin hydration process
US204677 1980-11-05

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EP0051328A1 EP0051328A1 (en) 1982-05-12
EP0051328B1 true EP0051328B1 (en) 1984-08-01

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EP (1) EP0051328B1 (en)
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Publication number Priority date Publication date Assignee Title
DE3583818D1 (en) * 1984-05-25 1991-09-26 Asahi Chemical Ind METHOD FOR PRODUCING A CYCLIC ALCOHOL.
US4595786A (en) * 1984-11-27 1986-06-17 E. I. Du Pont De Nemours And Company Hydration of cyclohexene in presence of perfluorosulfonic acid polymer
JPH0669979B2 (en) * 1985-11-22 1994-09-07 住友化学工業株式会社 Method for producing cycloalkanol
JPH07110821B2 (en) * 1987-04-08 1995-11-29 住友化学工業株式会社 Method for producing cycloalkanol
DE3829143A1 (en) * 1988-08-27 1990-03-01 Basf Ag METHOD FOR SEPARATING CYCLOHEXANOL
DE3829142A1 (en) * 1988-08-27 1990-03-01 Basf Ag METHOD FOR SEPARATING CYCLOHEXANOL
DE3829709A1 (en) * 1988-09-01 1990-03-15 Basf Ag METHOD FOR SEPARATING CYCLOHEXANOL FROM AQUEOUS SOLUTIONS CONTAINING SUCH AND AROMATIC SULPHONIC ACIDS
US5488185A (en) * 1993-09-30 1996-01-30 The Boc Group, Inc. Process for the production of ethanol and isopropanol
TW321634B (en) * 1994-07-05 1997-12-01 Mitsui Toatsu Chemicals
US6106675A (en) * 1998-07-24 2000-08-22 Battelle Memorial Institute Method of microwave bond cleavage of a hydrocarbon compound in a liquid phase
BRPI1014338B1 (en) 2009-06-25 2019-12-24 Shell Int Research method for injecting water in a formation containing hydrocarbons, and, method for preparing water with high salinity
WO2012061596A1 (en) 2010-11-05 2012-05-10 Shell Oil Company Treating biomass to produce materials useful for biofuels
US8900833B2 (en) * 2011-12-01 2014-12-02 Shell Oil Company Method of recovering lipids from microbial biomass
BR112014027355B1 (en) 2012-05-07 2020-12-29 Shell Internationale Research Maatschappij B.V. continuous or semi-continuous process to treat biomass

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Publication number Priority date Publication date Assignee Title
GB389133A (en) * 1931-09-11 1933-03-13 Henry Dreyfus Improvements in or relating to the direct hydration of olefines
GB409676A (en) * 1932-11-02 1934-05-02 Henry Dreyfus Improvements in or relating to the hydration of olefines
US2144750A (en) * 1934-03-05 1939-01-24 Shell Dev Process for the production of hydrated olefines
US2070258A (en) * 1934-04-18 1937-02-09 Dow Chemical Co Production of tertiary butyl alcohol
US2472618A (en) * 1944-02-05 1949-06-07 Albert A F Maxwell Production of ethyl alcohol
US2477380A (en) * 1946-08-30 1949-07-26 Atlantic Refining Co Production of tertiary aliphatic alcohols
US3257469A (en) * 1962-04-02 1966-06-21 Sinclair Research Inc Alcohols by selective hydrolysis of olefins
DE2007456A1 (en) * 1969-02-18 1970-09-10 American Cyanamid Company, Wayne, N.J. (V.St.A.) Production and isolation of lower aliphatic acids
IL47886A (en) * 1975-08-07 1978-03-10 Imi Inst For Research And Dev Production of isporopanol by gas phase hydration of propylene
GB1518461A (en) * 1976-05-13 1978-07-19 Shell Int Research Hydration of unsaturated compounds

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US4306101A (en) 1981-12-15
DE3165252D1 (en) 1984-09-06
EP0051328A1 (en) 1982-05-12

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